JP2018173466A - Photosensitive resin composition and method for manufacturing circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in insulation reliability of a formed resin pattern even when a coating film is thinned and to provide a method for manufacturing a circuit board using the composition.SOLUTION: The photosensitive resin composition comprises: (A) component: a resin having a phenolic hydroxyl group; (B) component: a compound having a methylol group or an alkoxyalkyl group; component (C): an aliphatic compound having two or more functional groups which are one or more kinds selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group; component (D): a photosensitive acid generator; and component (F): at least one kind of solvent selected from the group consisting of ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, lactic acid ester and γ-butyrolactone.SELECTED DRAWING: None

Description

  The present disclosure relates to a photosensitive resin composition and a method for producing a circuit board using the same.

  In the production of a semiconductor element or a printed wiring board, for example, a negative photosensitive resin composition is used to form a fine pattern. In this method, a photosensitive layer (coating film) is formed on a base material (a wafer in the case of a semiconductor element, a substrate in the case of a printed wiring board) by application of a photosensitive resin composition, etc., and an actinic ray through a predetermined pattern. The exposed area is cured by irradiation. Furthermore, the resin pattern which is a cured film of the photosensitive resin composition is formed on a base material by selectively removing an unexposed part using a developing solution. Therefore, the photosensitive resin composition is required to be excellent in sensitivity to actinic rays, ability to form a fine pattern (resolution), and the like. For example, Patent Document 1 discloses a photosensitive resin composition having excellent resolution.

  Patent Document 2 discloses a method for producing a circuit board having a further miniaturized conductor pattern using a photosensitive resin composition having excellent resolution.

International Publication No. 2015/046522 International Publication No. 2016/084855

  By the way, it is generally known that the resolution of the coating film formed from the photosensitive resin composition is improved when the thickness is reduced. For this reason, when it is going to improve the resolution of the photosensitive resin composition, it is desirable to make a coating film thin. In consideration of the adhesion between the substrate and the resin pattern, the coating film is preferably thin. On the other hand, when an attempt is made to apply the photosensitive resin composition to the circuit board manufacturing method, insulation reliability of the formed resin pattern is required. However, as a result of intensive studies, the present inventors have reduced the thickness of the coating film formed from the conventional photosensitive resin composition prepared in Patent Documents 1 and 2, etc. (for example, about 5 μm), It was found that sufficient insulation reliability could not be obtained.

  Then, even if it is a case where a coating film is made thin, this indication aims at providing the manufacturing method of the photosensitive resin composition excellent in the insulation reliability of the resin pattern formed, and a circuit board using the same. .

In view of the above circumstances, the present disclosure provides the following inventions.
[1] Component (A): a resin having a phenolic hydroxyl group,
(B) component: a compound having a methylol group or an alkoxyalkyl group,
(C) component: an aliphatic compound having two or more functional groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group,
(D) component: Photosensitive acid generator, and
(F) Component: Photosensitive resin composition containing at least one solvent selected from the group consisting of ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, lactic acid ester and γ-butyrolactone.
[2] Component (E): The photosensitive resin composition according to [1], further comprising a compound having a Si—O bond.
[3] The photosensitive resin composition according to [2], wherein the component (E) is a silane coupling agent.
[4] (a) Applying the photosensitive resin composition according to any one of [1] to [3] on a substrate and drying the photosensitive resin composition to form a photosensitive layer;
(B) exposing the photosensitive layer in a predetermined pattern, developing, and further heat-treating to obtain a resin pattern;
(C) forming a conductor layer by plating the exposed portion of the substrate and the exposed portion of the resin pattern;
(D) removing a part of the conductor layer to form a conductor pattern;
A method of manufacturing a circuit board comprising:

  According to this indication, even if it is a case where a coating film is made thin, the photosensitive resin composition which is excellent in the insulation reliability of the resin pattern formed, and the manufacturing method of a circuit board using the same can be provided.

It is a schematic cross section showing a manufacturing method of a circuit board concerning one embodiment of this indication.

  Hereinafter, although an embodiment of the present disclosure will be specifically described, the present disclosure is not limited thereto. In the following embodiment, it is needless to say that its constituent elements (including element steps and the like) are not necessarily essential unless otherwise specified or apparently essential in principle. . This also applies to numerical values and ranges, and should not be construed to unduly limit the present disclosure.

  In this specification, the terms “layer” and “film” refer to a structure formed in part in addition to a structure formed over the entire surface when observed as a plan view. Is included. The term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. “EO-modified” means a compound having a (poly) oxyethylene group, and “PO-modified” means a compound having a (poly) oxypropylene group. Here, “(poly) oxyethylene group” means at least one of an oxyethylene group and a polyoxyethylene group in which two or more ethylene groups are linked by an ether bond. The “(poly) oxypropylene group” means at least one of an oxypropylene group and a polyoxypropylene group in which two or more propylene groups are linked by an ether bond. The term “Si—O bond” indicates a bond between a silicon atom and an oxygen atom, and may be a part of a siloxane bond (Si—O—Si bond). The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. “A or B” only needs to include either A or B, and may include both. The materials exemplified below can be used singly or in combination of two or more unless otherwise specified. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

(Photosensitive resin composition)
The photosensitive resin composition of the present embodiment comprises (A) component: resin having a phenolic hydroxyl group, (B) component: a compound having a methylol group or an alkoxyalkyl group, and (C) component: acryloyloxy group, methacryloyloxy group. , An aliphatic compound having two or more functional groups selected from a glycidyloxy group and a hydroxyl group, (D) component: a photosensitive acid generator, and (F) component: ethylene glycol monoalkyl ether It contains at least one solvent selected from the group consisting of acetate, propylene glycol monoalkyl ether acetate, lactic acid ester and γ-butyrolactone. The photosensitive resin composition of this embodiment may further contain component (E): a compound having a Si—O bond, and the like. Hereinafter, each component will be described.

<(A) component>
Although it does not specifically limit as resin which has the phenolic hydroxyl group which is (A) component, It is preferable that it is resin soluble in alkaline aqueous solution, and a novolak resin is especially preferable. Such a novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples include trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

  Specific examples of such novolak resins include phenol / formaldehyde condensed novolak resins, cresol / formaldehyde condensed novolak resins, phenol-naphthol / formaldehyde condensed novolak resins, and the like.

  Examples of the component (A) other than the novolak resin include polyhydroxystyrene and copolymers thereof, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, and the like. It is done. (A) A component can be used individually by 1 type or in mixture of 2 or more types.

  The component (A) preferably has a weight average molecular weight of 100,000 or less, preferably 1000 to 80,000, from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance and the like of the cured film obtained. More preferably, it is more preferably 2000 to 50000, particularly preferably 2000 to 20000, and most preferably 5000 to 15000.

  In the photosensitive resin composition of the present embodiment, the content of the component (A) is 30 to 90 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition (excluding the solvent). Preferably, it is 40-80 mass parts. When the content of the component (A) is within this range, a film formed using the resulting photosensitive resin composition tends to have further developability with an alkaline aqueous solution.

<(B) component>
The photosensitive resin composition of this embodiment contains the compound which has a methylol group or an alkoxyalkyl group as (B) component. The component (B) is preferably a compound further having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring. Here, the aromatic ring means an aromatic hydrocarbon group (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic ring means a cyclic group (for example, a cyclic group having 3 to 10 carbon atoms) having at least one hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom, such as a pyridine ring, an imidazole ring, Examples include a pyrrolidinone ring, an oxazolidinone ring, an imidazolidinone ring and a pyrimidinone ring. The alicyclic ring means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and A cyclohexane ring is mentioned. An alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group through an oxygen atom. Further, the two alkyl groups may be different from each other, for example, an alkyl group having 1 to 10 carbon atoms.

  By containing the component (B), when the photosensitive layer after the resin pattern is formed is heated and cured, the component (B) reacts with the component (A) to form a bridge structure, and the resin pattern is weak. And deformation of the resin pattern can be prevented, and heat resistance can be improved. Specifically, a compound further having a phenolic hydroxyl group or a compound further having a hydroxymethylamino group can be preferably used, and the component (A) and the component (C) are not included. (B) A component can be used individually by 1 type or in mixture of 2 or more types.

  As will be described later, by including the component (D) in the photosensitive resin composition, an acid is generated by irradiation with actinic rays or the like. Due to the catalytic action of the generated acid, the alkoxyalkyl groups in component (B) or the alkoxyalkyl groups in component (B) react with component (A) with dealcoholization to form a negative pattern. can do. Further, due to the catalytic action of the generated acid, the methylol groups in the component (B) or the methylol groups in the component (B) react with the component (A) with dealcoholization to form a negative pattern. Can be formed.

  The compound further having a phenolic hydroxyl group has a phenolic hydroxyl group in addition to a methylol group or an alkoxyalkyl group, so that not only the reaction with the component (C) or the component (A) but also the development with an alkaline aqueous solution. It is possible to increase the dissolution rate of the unexposed part of the film and improve the sensitivity. The molecular weight of the compound having a phenolic hydroxyl group is preferably 94 to 2000 in terms of weight average molecular weight in consideration of improving the solubility in aqueous alkali solution, photosensitivity, mechanical properties and the like in a balanced manner, and 108 to 2000. More preferably, it is 108-1500.

一般式（１）中、Ｚは単結合又は２価の有機基を示し、Ｒ_２４及びＲ_２５はそれぞれ独立に水素原子又は１価の有機基を示し、Ｒ_２６及びＲ_２７はそれぞれ独立に１価の有機基を示し、ａ及びｂはそれぞれ独立に１〜３の整数を示し、ｃ及びｄはそれぞれ独立に０〜３の整数を示す。ここで、１価の有機基としては、例えば、メチル基、エチル基、プロピル基等の炭素原子数が１〜１０であるアルキル基；ビニル基等の炭素原子数が２〜１０であるアルケニル基；フェニル基等の炭素原子数が６〜３０であるアリール基；これら炭化水素基の水素原子の一部又は全部をフッ素原子等のハロゲン原子で置換した基が挙げられる。 As the compound further having a phenolic hydroxyl group, a conventionally known compound can be used, and the compound represented by the following general formula (1) is effective in promoting the dissolution of the unexposed area and curing the photosensitive resin film. It is preferable because it is excellent in the balance of the effect of preventing melting of the resin.

In general formula (1), Z represents a single bond or a divalent organic group, R ₂₄ and R ₂₅ each independently represent a hydrogen atom or a monovalent organic group, and R ₂₆ and R ₂₇ each independently represent 1 A valent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently represents an integer of 0 to 3. Here, examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, and a propyl group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group. An aryl group having 6 to 30 carbon atoms such as a phenyl group; a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom.

一般式（２）中、Ｘ_１は単結合又は２価の有機基を示し、Ｒはアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。 The compound represented by the general formula (1) is preferably a compound represented by the general formula (2).

In General Formula (2), X ₁ represents a single bond or a divalent organic group, and R represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

一般式（３）中、Ｒはアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。 Moreover, you may use the compound represented by General formula (3) as a compound which has the said phenolic hydroxyl group.

In general formula (3), R represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

  In the general formula (1), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by Z include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group; an alkylidene having 2 to 10 carbon atoms such as an ethylidene group. An arylene group having 6 to 30 carbon atoms such as a phenylene group; a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms; a sulfonyl group; a carbonyl group; an ether bond A sulfide bond; an amide bond and the like. Among these, Z is preferably a divalent organic group represented by the following general formula (4).

一般式（４）中、Ｘ_２は、単結合、アルキレン基（例えば、炭素原子数が１〜１０のアルキレン基）、アルキリデン基（例えば、炭素原子数が２〜１０のアルキリデン基）、それらの水素原子の一部又は全部をハロゲン原子で置換した基、スルホニル基、カルボニル基、エーテル結合、スルフィド結合又はアミド結合を示す。Ｒ_２８は、水素原子、水酸基、アルキル基（例えば、炭素原子数が１〜１０のアルキル基）又はハロアルキル基を示し、ｅは１〜１０の整数を示す。複数のＲ_２８は互いに同一でも異なっていてもよい。ここで、ハロアルキル基とは、ハロゲン原子で置換されたアルキル基を意味する。

In general formula (4), X ₂ represents a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), A group in which part or all of the hydrogen atoms are substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond or an amide bond is shown. R ₂₈ represents a hydrogen atom, a hydroxyl group, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms) or a haloalkyl group, and e represents an integer of 1 to 10. The plurality of R ₂₈ may be the same as or different from each other. Here, the haloalkyl group means an alkyl group substituted with a halogen atom.

  Examples of the compound further having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) ( N-hydroxymethyl) urea and the like. Moreover, you may use the nitrogen-containing compound etc. which alkyl-etherified all or one part of the hydroxymethylamino group of these compounds. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea and the like.

一般式（５）中、Ｒはアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。

一般式（６）中、Ｒはアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。 Specifically, the compound having a hydroxymethylamino group is preferably a compound represented by the general formula (5) or a compound represented by the general formula (6).

In the general formula (5), R represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

In General Formula (6), R represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

  The content of the component (B) is preferably 5 to 60 parts by mass, more preferably 10 to 45 parts by mass, and 10 to 35 parts by mass with respect to 100 parts by mass of the component (A). It is particularly preferred. When the content of the component (B) is 5 parts by mass or more, the reaction of the exposed part becomes sufficient, so that the resolution is hardly deteriorated and the chemical resistance and heat resistance tend to be good, and 60 parts by mass. Or less, the photosensitive resin composition tends to be easily formed on a desired support and the resolution tends to be good.

<(C) component>
Component (C): an aliphatic compound having two or more functional groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group is a photosensitive resin composition and a support. To improve the tackiness, i.e., tackiness. Furthermore, it is possible to increase the dissolution rate of the unexposed area when developing with an alkaline aqueous solution, thereby improving the resolution. From the viewpoint of tackiness and solubility in an aqueous alkali solution, the molecular weight of the component (C) is preferably 92 to 2000, more preferably 106 to 1500 in terms of weight average molecular weight in consideration of balance, and 134 to 1300 is particularly preferable. The “aliphatic compound” refers to a compound in which the main skeleton is an aliphatic skeleton and does not contain an aromatic ring or a heterocyclic ring.

［一般式（７）〜（１０）中、Ｒ_１、Ｒ_５、Ｒ_１６及びＲ_１９は、それぞれ水素原子、メチル基、エチル基、水酸基又は一般式（１１）で表される基を示し、Ｒ_２１は水酸基、グリシジルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を示し、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４、Ｒ_１５、Ｒ_１７、Ｒ_１８及びＲ_２０は、それぞれ水酸基、グリシジルオキシ基、アクリロイルオキシ基、メタクリロイルオキシ基、一般式（１２）で表される基又は一般式（１３）で表される基を示し、Ｒ_２２及びＲ_２３はそれぞれ水酸基、グリシジルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を示し、ｎ及びｍはそれぞれ１〜１０の整数である。］ The functional group of component (C) is preferably a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, more preferably a glycidyloxy group or an acryloyl group, and even more preferably an acryloyloxy group. Moreover, it is preferable that (C) component has 3 or more of the said functional groups. The upper limit of the number of functional groups is not particularly limited, but is 12 for example. Specific examples of the component (C) include compounds represented by general formulas (7) to (10).

[In General Formulas (7) to (10), R ₁ , R ₅ , R ₁₆ and R ₁₉ each represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by General Formula (11), R ₂₁ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and R ₂ , R ₃ , R ₄ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₇ , R ₁₈ and R ₂₀ are each a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the general formula (12), or the general formula (13). a group represented, respectively, R ₂₂ and R ₂₃ represents a hydroxyl group, a glycidyloxy group, acryloyloxy group or methacryloyloxy indicates an oxy group, an integer der respectively n and m 1 to 10 . ]

  Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl. Ether, glycerin diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, Glycerol propoxylay Triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, and the like diglycidyl 1,2-cyclohexane dicarboxylate. These compounds having a glycidyloxy group can be used singly or in combination of two or more.

  Among the compounds having a glycidyloxy group, trimethylolethane triglycidyl ether or trimethylolpropane triglycidyl ether is preferable in terms of excellent sensitivity and resolution.

  The compound having a glycidyloxy group is, for example, Epolite 40E, Epolite 100E, Epolite 70P, Epolite 200P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (above, Kyoeisha Chemical Co., Ltd., trade name), alkyl type epoxy Resin ZX-1542 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, and Denacol EX-850L (above, Nagase Chemtech Co., Ltd.) (Commercially available as product name).

  Examples of the compound having an acryloyloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, ditrimethylolpropane. Tetraacrylate, EO modified pentaerythritol tetraacrylate, PO modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO modified pentaerythritol triacrylate, PO modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO modified trimethylolpropane acrylate, PO modified Trimethylol B bread acrylate, trimethylolpropane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. These compounds having an acryloyloxy group can be used singly or in combination of two or more. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

  Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, and ditrimethylolpropane. Tetramethacrylate, EO-modified pentaerythritol tetramethacrylate, PO-modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO-modified pentaerythritol trimethacrylate, PO-modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO-modified trimethylolpropane methacrylate DOO, PO-modified trimethylolpropane dimethacrylate, trimethylolpropane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. These compounds having a methacryloyloxy group can be used singly or in combination of two or more. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

  Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol, and glycerin. These compounds having a hydroxyl group can be used singly or in combination of two or more.

  The content of component (C) is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, and preferably 35 to 55 parts by mass with respect to 100 parts by mass of component (A). It is particularly preferred. If the content of the component (C) is 20 parts by mass or more, there is a tendency that crosslinking in the exposed part is sufficient and tackiness is sufficient, and if it is 70 parts by mass or less, the photosensitive resin composition is supported as desired. It becomes easy to form a film on the body, and the resolution is not easily lowered.

<(D) component>
The photosensitive acid generator which is (D) component is a compound which generate | occur | produces an acid by irradiation of actinic rays. Further, not only the (B) components react with each other by the generated acid, but also the (B) component reacts with the (A) component or the (C) component, thereby reducing the solubility of the photosensitive resin composition in the developer. By doing so, a negative pattern can be formed. In the case where the component (C) is a compound having an acryloyloxy group or a methacryloyloxy group, radical polymerization of the acryloyloxy group or methacryloyloxy group also proceeds by irradiation with an actinic ray or the like.

  The component (D) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or the like. Etc. Among them, it is preferable to use an onium salt compound or a sulfonimide compound from the viewpoint of availability. In particular, an onium salt compound is preferably used from the viewpoint of solubility in a solvent. Specific examples are shown below.

Onium salt compounds:
Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Preferred examples of the onium salt compound include diaryl iodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diaryliodonium salts such as diphenyliodonium tetrafluoroborate; triphenylsulfonium Triarylsulfonium salts such as trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p- Toluenesulfonate; 4, 7 And di -n- butoxy naphthyl tetrahydrothiophenium trifluoromethanesulfonate, and the like.

Sulfonimide compounds:
Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (p-toluenesulfonyloxy) -1,8- Naphthalimide and N- (10-camphorsulfonyloxy) -1,8-naphthalimide are mentioned.

  In the present embodiment, the component (D) is preferably a compound having a trifluoromethanesulfonate group, a hexafluoroantimonate group, a hexafluorophosphate group, or a tetrafluoroborate group, in that the sensitivity and resolution are further improved. . Moreover, (D) component can be used individually by 1 type or in mixture of 2 or more types.

  The content of the component (D) is 0. From 100 parts by mass of the component (A) from the viewpoint of improving the sensitivity, resolution, pattern shape, and the like of the photosensitive resin composition of the present embodiment. It is preferably 1 to 15 parts by mass, and more preferably 0.3 to 10 parts by mass.

<(E) component>
The photosensitive resin composition of this embodiment may contain the compound which has a Si-O bond as (E) component. The compound having a Si—O bond may be a compound having a siloxane bond. The component (E) is not particularly limited as long as it has a Si—O bond, and examples thereof include silica (silica filler) and silane compounds (such as a silane coupling agent). (E) A component can be used individually by 1 type or in mixture of 2 or more types.

  When the photosensitive resin composition of this embodiment contains an inorganic filler, the thermal expansion coefficient of a resin pattern can be reduced. When an inorganic filler is used as the component (E), the inorganic filler is preferably silica such as fused spherical silica, fused pulverized silica, fumed silica, or sol-gel silica. Moreover, the inorganic filler may have a Si-O bond by processing an inorganic filler with a silane compound. Among inorganic fillers treated with a silane compound, as inorganic fillers other than silica, aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, or talc, Examples include inorganic fillers derived from mineral products such as mica.

  The average primary particle diameter of the inorganic filler is preferably 100 nm or less, more preferably 80 nm or less, and further preferably 50 nm or less from the viewpoint of further improving the photosensitivity of the photosensitive layer. When the average primary particle size is 100 nm or less, the photosensitive resin composition is less likely to become cloudy, and light for exposure is easily transmitted through the photosensitive layer. As a result, since the unexposed part is easily removed, the resolution of the resin pattern tends to be difficult to decrease. The average primary particle diameter is a value obtained by converting from the BET specific surface area.

The thermal expansion coefficient of silica is preferably 5.0 × 10 ⁻⁶ / ° C. or less. Silica is preferably silica such as fused spherical silica, fumed silica, sol-gel silica, and more preferably fumed silica or sol-gel silica from the viewpoint of easily obtaining a suitable particle size. Moreover, it is preferable that a silica is a silica (nanosilica) with an average primary particle diameter of 5-100 nm.

  When measuring the particle size of the inorganic filler, a known particle size distribution meter can be used. The particle size distribution meter is a laser diffraction scattering type particle size distribution meter that calculates the particle size distribution by irradiating the particle group with laser light and calculating from the intensity distribution pattern of the diffracted light and scattered light emitted from the particle group; Examples thereof include a particle size distribution meter of nanoparticles for obtaining a particle size distribution using frequency analysis.

  When the photosensitive resin composition of this embodiment contains a silane compound, the adhesive strength between the photosensitive layer and the substrate after pattern formation can be improved. When a silane compound is used as the component (E), the silane compound is not particularly limited as long as the silane compound has a Si—O bond. Examples of the silane compound include alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane, styryl silane, alkyl chlorosilane, and the like.

(E) As a silane compound which is a component, the compound represented by following General formula (14) is preferable.
(R ¹⁰¹ O) _4-f -Si- (R ¹⁰² ) _f (14)

In General Formula (14), R ¹⁰¹ represents an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, or a propyl group, R ¹⁰² represents a monovalent organic group, and f represents An integer of 0 to 3 is shown. When f is 0, 1 or 2, the plurality of R ¹⁰¹ may be the same as or different from each other. When f is 2 or 3, the plurality of R ¹⁰² may be the same as or different from each other. R ¹⁰¹ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, from the viewpoint of further improving resolution. In the case of treating with a silane compound (such as a compound represented by the general formula (14)) in order to improve the dispersibility of the inorganic filler, f is preferably 0 to 2 from the viewpoint of further improving the dispersibility of the inorganic filler. 0 to 1 are more preferable.

  Specific examples of the (E) component silane compound include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and diisopropyl. Dimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylsilanol, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3 Aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3 -(Triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-methacryloyloxyp Pyrtrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- ( 1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane and the like. The component (E) is preferably a silane coupling agent, more preferably an epoxy silane having one or more glycidyloxy groups, and an epoxy silane having a trimethoxysilyl group or a triethoxysilyl group. Further preferred.

  As for content of (E) component, 1.8-420 mass parts is preferable with respect to 100 mass parts of (A) component, and 1.8-270 mass parts is more preferable. (E) Content of a component may be 1-20 mass parts with respect to 100 mass parts of (A) component, and may be 3-10 mass parts.

<(F) component>
The photosensitive resin composition of this embodiment contains at least one solvent selected from the group consisting of ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, lactic acid ester and γ-butyrolactone as component (F). To do. By using these solvents, it is not always clear why a highly reliable device can be manufactured in a high humidity environment even when the resolution is good and the coating film thickness is reduced. However, the influence of these solvents on the components (A) to (D) is extremely small, and it has a constant boiling point, preventing the strength of the coating from decreasing due to volatilization of the solvent when forming the coating. Possible points are considered to be part of the reason.

  Examples of the alkyl group in ethylene glycol monoalkyl ether acetate and propylene glycol monoalkyl ether acetate include a methyl group, an ethyl group, an n-propyl group, and isopropyl, and a methyl group, an ethyl group, or an n-propyl group is preferable. Preferably, a methyl group or an ethyl group is more preferable.

  Examples of the lactic acid ester include methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate, and methyl lactate or ethyl lactate is preferable, and ethyl lactate is more preferable.

  The component (F) is preferably ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate or lactic acid ester from the viewpoint of improving the insulation reliability of the resin pattern to be formed, and propylene glycol monoalkyl ether acetate or lactic acid. An ester is more preferable, and propylene glycol monomethyl ether acetate or ethyl lactate is still more preferable.

  The content of the component (F) is preferably 30 to 200 parts by mass and more preferably 60 to 120 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (F). preferable.

  The photosensitive resin composition of the present embodiment is a solvent other than the component (F), for example, propylene glycol monoalkyl such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether. Ethers; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; cellosolves such as ethyl cellosolve and butyl cellosolve; ethyl carbitol acetate such as butyl carbitol; -Propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate Aliphatic carboxylic acid esters such as isopropyl propionate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Other esters such as methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; and ketones such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone In that case, the content of the solvent other than the component (F) is preferably 50% by mass or less, more preferably 25% by mass or less, and substantially no content ((F) component). For example, 2% by mass or less) is more preferable.

  In addition, the photosensitive resin composition of this embodiment may contain other components other than the above-mentioned component. Examples of other components include a colorant, an adhesion assistant, a leveling agent, an inorganic filler having no Si—O bond, a reaction inhibitor accompanying irradiation with actinic rays, and an adhesion assistant.

(Circuit board manufacturing method)
FIG. 1 is a diagram illustrating a method for manufacturing a circuit board according to an embodiment of the present disclosure. The circuit board manufacturing method according to the present embodiment includes (a) a step of applying the above-described photosensitive resin composition onto the substrate 1, drying the photosensitive resin composition to form the photosensitive layer 2, and ( b) The photosensitive layer 2 is exposed in a predetermined pattern, developed, and further subjected to heat treatment to obtain a resin pattern 4; and (c) the exposed portion of the substrate 1 and the exposed portion of the resin pattern 4 are plated. Thus, the method includes the step of forming the conductor layer 7 and the step (d) of removing a part of the conductor layer 7 to form the conductor pattern 8 (circuit). That is, the circuit board manufacturing method according to the present embodiment is a method for manufacturing a circuit board including the resin pattern 4 formed using a predetermined pattern and the miniaturized conductor pattern 8 on the substrate 1. . Here, the resin pattern is a resin pattern obtained by curing a photosensitive layer on which a predetermined pattern is formed, and part or all of the resin in the resin pattern is cured.

  Hereinafter, each process will be described in detail.

<(A) Process>
Step (a) is a step in which the photosensitive resin composition described above is applied onto the substrate 1 and the photosensitive resin composition is dried to form the photosensitive layer 2 (see FIG. 1A). That is, the step (a) can be said to be a step of obtaining a substrate provided with the photosensitive layer 2 containing the photosensitive resin composition.

  Examples of the method for applying the photosensitive resin composition to the substrate include a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method. The thickness of the coating film can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the photosensitive resin composition. The thickness of the photosensitive layer 2 varies depending on the use, but the thickness of the photosensitive layer 2 after drying is preferably 1 to 100 μm, more preferably 2 to 60 μm, and further preferably 3 to 25 μm. It is especially preferable that it is 4-8 micrometers.

  As the substrate 1, for example, a resin-coated copper foil, a copper clad laminate, a silicon wafer with a metal sputtered film, or an alumina substrate can be used. Moreover, the surface in which the photosensitive layer 2 in the board | substrate 1 is formed may be a cured resin layer formed using the photosensitive resin composition. In that case, there exists a tendency for adhesiveness with a base material to improve.

<(B) Process>
The step (b) is a step of obtaining the resin pattern 4 by exposing the photosensitive layer 2 with a predetermined pattern, developing, and further heat-treating (see FIGS. 1B and 1C).

First, the photosensitive layer 2 is exposed with a predetermined pattern through a predetermined mask pattern. Examples of the actinic light used for exposure include light using a g-line stepper as a light source; ultraviolet light using a low-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, i-line stepper or the like as a light source; electron beam; The exposure amount is appropriately selected depending on the light source used, the thickness of the coating film, and the like. For example, when the coating film having a thickness of 10 to 50 μm is irradiated with ultraviolet rays using a high-pressure mercury lamp, the exposure amount is 100 to 5000 mJ / it may be a cm ^2.

  Next, the exposed photosensitive layer 2 is developed with an alkaline developer, and a region (unexposed portion) other than the portion cured by exposure is dissolved and removed to obtain the photosensitive layer 2 on which a predetermined pattern is formed. (See FIG. 1 (b)). The region removed here becomes a region (circuit groove 3) where the conductor pattern 8 is to be formed. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The development conditions are usually 20 to 40 ° C. and 1 to 10 minutes.

  Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline is dissolved in water so that the concentration is about 1 to 10% by mass, aqueous ammonia, and the like. An alkaline aqueous solution or the like can be used. Among them, it is preferable to use an aqueous tetramethylammonium hydroxide solution in terms of excellent resolution of the resin pattern 4. For example, a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution. In addition, after developing with an alkaline developer, it is washed with water and dried.

  Next, a resin pattern 4 is obtained by heat-treating the photosensitive layer 2 on which a predetermined pattern is formed (see FIG. 1C). By performing the heat treatment, the insulating film characteristics are exhibited. The conditions for the heat treatment are not particularly limited, and can be adjusted according to the use of the cured product. For example, the heating temperature may be 50 to 250 ° C. and the heating time may be 30 minutes to 10 hours.

  Further, the heat treatment may be performed in two stages for the purpose of sufficiently proceeding curing, preventing deformation of the shape of the obtained resin pattern 4 and the like. When performing the heat treatment in two stages, for example, the first stage heating temperature and heating time are 50 to 120 ° C. and 5 minutes to 2 hours, respectively, and the second stage heating temperature and heating time are 80 to 200 ° C. and It can be 10 minutes to 10 hours.

  When performing the heat treatment under the above-described conditions, the heating equipment is not particularly limited, and for example, a general oven or an infrared furnace can be used.

  In the method for manufacturing a circuit board according to this embodiment, heat treatment (post-exposure baking) may be performed before post-exposure development. The post-exposure baking conditions vary depending on the content of the photosensitive resin composition, the thickness of the coating film, etc., but it is usually preferable to heat at 70 to 150 ° C. for 1 to 60 minutes, and 1 to 60 at 80 to 120 ° C. It is more preferable to heat for a minute.

<(C) Process>
(C) A process is a process of forming the conductor layer 7 by plating the exposed part of the board | substrate 1 and the exposed part of the resin pattern 4 (refer FIG.1 (d) and (e)). In addition, the exposed part of the board | substrate 1 is an area | region in which the resin pattern is not formed in the surface in which the resin pattern of the board | substrate 1 is formed.

  The method for the plating treatment is not particularly limited, and for example, a method using electrolytic plating, electroless plating, or sputtering may be used.

  Although the thickness of the conductor layer 7 can be appropriately adjusted according to the height of the wiring groove to be formed, it is preferably 1 to 35 μm, and more preferably 3 to 25 μm.

  The conductor layer 7 may be composed of a seed metal layer 5 and a plating layer 6 grown thereon. That is, the step (c) may include a step of forming the seed metal layer 5 on the exposed portion of the substrate 1 and the exposed portion of the resin pattern 4 (see FIG. 1D). When the seed metal layer 5 is formed, the plating layer 6 can be formed by plating the formed seed metal layer 5 (see FIG. 1E).

  Although it does not specifically limit as a formation method of the seed metal layer 5, For example, electroless plating and sputtering are mentioned.

  When the seed metal layer 5 is formed by electroless plating, the metal constituting the seed metal layer 5 is, for example, gold, platinum, silver, copper, aluminum, cobalt, chromium, nickel, titanium, tungsten, iron, tin, indium It may be a simple metal such as nickel or a solid solution (alloy) of two or more kinds of metals such as nickel / chromium alloy. Among these, the metal constituting the seed metal layer 5 is chromium, nickel, titanium, nickel / chromium alloy, aluminum, zinc, copper / copper, from the viewpoint of versatility of metal film formation, cost, ease of removal by etching, and the like. It is preferably nickel alloy, copper / titanium alloy, gold, silver or copper, more preferably chromium, nickel, titanium, nickel / chromium alloy, aluminum, zinc, gold, silver or copper, and titanium or copper. It is particularly preferred. The seed metal layer 5 may be a single layer or a multilayer structure in which two or more different metals are stacked.

  When the seed metal layer 5 is formed by electroless plating, an electroless plating solution is used. As the electroless plating solution, a known autocatalytic electroless plating solution can be used, and the metal species, reducing agent species, complexing agent species, hydrogen ion concentration, dissolved oxygen concentration contained in the electroless plating solution. Etc. are not particularly limited. As electroless plating, for example, electroless copper plating solution using ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as a reducing agent; electroless using sodium hypophosphite as a reducing agent Nickel-phosphorous plating solution; electroless nickel-boron plating solution using dimethylaminoborane as a reducing agent; electroless palladium plating solution; electroless palladium-phosphorous plating solution using sodium hypophosphite as a reducing agent; electroless gold plating An electroless silver plating solution; an electroless nickel-cobalt-phosphorous plating solution using sodium hypophosphite as a reducing agent can be used.

  In addition, the method of forming the seed metal layer 5 by electroless plating is, for example, a method in which a catalyst nucleus such as silver, palladium, zinc, or cobalt is attached to the portion where the seed metal layer 5 is formed, and then the above-described electroless plating is performed. It may be a method of forming a metal thin film on the catalyst core using a liquid.

  The method for attaching the catalyst nucleus to the exposed portion of the substrate 1 and the exposed portion of the resin pattern 4 is not particularly limited. For example, a solution in which a metal compound, salt or complex of a metal serving as a catalyst nucleus is dissolved in water or an organic solvent (for example, alcohol and chloroform) so as to have a concentration of 0.001 to 10% by mass is prepared. There is a method in which after the substrate 1 on which the resin pattern 4 is formed is immersed in this solution, the metal in the solution is reduced to precipitate the metal. In addition, an acid, an alkali, a complexing agent, a reducing agent, etc. can be contained in the solution in the said method as needed.

  When the seed metal layer 5 is formed by sputtering, for example, the same metal as that used to form the seed metal layer 5 by electroless plating can be used as the metal constituting the seed metal layer 5.

  Although the metal which comprises the plating layer 6 is not specifically limited, It is preferable that it is copper. Examples of the method for forming the plating layer 6 on the seed metal layer 5 include a method in which plating is grown by wet plating such as electrolytic plating.

  When the seed metal layer 5 is formed, the seed metal layer 5 can be subjected to rust prevention treatment using a rust preventive agent after the seed metal layer 5 is formed and before the plating layer 6 is formed.

  When the seed metal layer 5 is formed, the thickness of the seed metal layer 5 is not particularly limited, but is preferably 10 nm to 5000 nm, more preferably 20 nm to 2000 nm, and more preferably 30 nm to 1000 nm. More preferably, it is 50 nm-500 nm, It is especially preferable that it is 50 nm-300 nm. When the thickness is 10 nm or more, the plating layer 6 tends to be formed uniformly by electrolytic plating. When the thickness is 5000 nm or less, the removal time of the seed metal layer by etching or polishing is appropriately shortened. Therefore, the cost for removing the seed metal layer 5 can be suppressed.

  After the formation of the conductor layer 7, the conductor layer 7 may be heated for the purpose of improving adhesion or the like. The heating temperature is usually 50 to 350 ° C, preferably 80 to 250 ° C. In addition, you may implement heating on pressurization conditions. Examples of the pressurizing method include a method using physical pressurizing means such as a hot press machine and a pressurizing and heating roll machine. The applied pressure is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. Within this range, the adhesion between the seed metal layer 5 and the resin pattern 4 or the substrate 1 tends to be excellent.

<(D) Process>
Step (d) is a step in which a part of the conductor layer 7 is removed to form the conductor pattern 8 (see FIG. 1 (f)). As shown in FIG. 1 (e), the conductor layer 7 is formed on the entire exposed portion of the substrate 1 and the exposed portion of the resin pattern 4. That is, plating (metal film) is also formed in a region other than the region where the conductor pattern 8 is to be formed (circuit groove 3). Therefore, the step (d) can be said to be a step of removing a metal film formed in a region other than the circuit groove 3 in the conductor layer 7.

  The method for removing a part of the conductor layer 7 may be a known method for removing metal. For example, a mechanical polishing method and / or an etching method may be used.

  When part of the conductor layer 7 is removed by mechanical polishing, the mechanical polishing method is preferably a chemical mechanical polishing (hereinafter, also referred to as “CMP”) method. The method of removing a part of the conductor layer 7 by the CMP method is, for example, attaching a polishing cloth (polishing pad) on a polishing platen (platen), immersing the surface of the polishing cloth with a metal abrasive, The surface is pressed against the surface of the polishing cloth, and a predetermined surface pressure (hereinafter referred to as “polishing pressure”) is applied to the surface of the conductor layer 7 while the polishing platen is turned. A part of the conductor layer 7 may be removed by mechanical friction.

  The metal abrasive used in CMP may contain, for example, an oxidizer and solid abrasive grains (hereinafter simply referred to as “abrasive grains”), and if necessary, a metal oxide solubilizer and a protective film. It may further contain a forming agent or the like. The basic mechanism of CMP using an abrasive containing an oxidizing agent and abrasive grains is considered as follows. First, it is considered that the surface of a metal film to be polished is oxidized by an oxidizing agent to form an oxide layer, and the oxide film is scraped off by abrasive grains to polish the metal film. When polished by such a mechanism, the oxide layer on the surface of the metal film formed in the circuit groove 3 does not touch the polishing cloth so much, and the metal film formed in the circuit groove 3 has an effect of scraping off by abrasive grains. It is difficult. Therefore, polishing by CMP proceeds and the metal film in the region other than the circuit groove 3 is removed and the polished surface tends to be flattened.

  The abrasive is preferably an abrasive that can be used at a polishing rate in the range of 5000 to 3000 kg / min.

  When part of the conductor layer 7 is removed by etching, examples of the etching method include a sand blast method and a wet etching process. In the case of the sandblasting method, for example, etching is performed by spraying cutting particles such as silica and alumina onto a portion of the conductor layer 7 to be removed. In the case of a wet etching process, etching is performed using an etching solution. As an etching solution, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, an aqueous ammonium persulfate solution, and a hydrogen peroxide etching solution can be used.

  Of the conductor layer 7, the thickness of the metal film in the portion removed in the step (d), that is, the region other than the circuit groove 3 may be about 0.1 to 35 μm.

  In the circuit board manufactured by the above method, a semiconductor element is mounted at a corresponding position, and electrical connection can be ensured. In addition, a circuit board having a miniaturized conductor pattern 8 can be obtained by the above method.

  Hereinafter, although an example and an advantage of this indication are explained in detail by an example, this indication is not limited at all by these examples.

[Examples 1-2 and Comparative Examples 1-2]
<Preparation of photosensitive resin composition>
The compound (B-1) having an alkoxyalkyl group, the compound (C-1) having a glycidyloxy group, and a photosensitive acid generator with respect to 100 parts by mass of the resin component (A-1) having a phenolic hydroxyl group (D-1), the compound (E-1) having a Si—O bond, and the solvents (F-1 to F-4) in the compounding amounts (unit: parts by mass) shown in Table 1. The photosensitive resin composition was obtained by blending.

Abbreviations in Table 1 are as follows.
A-1: Cresol novolak resin (Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 13000)
B-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak MX-270)
C-1: Trimethylolpropane triglycidyl ether (Nagase ChemteX Corporation, trade name: EX-321L)
D-1: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B, anion: tetrakis (pentafluorophenyl) borate)
E-1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403)
F-1: Propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 2-methoxy-1-methylethyl acetate)
F-2: Ethyl lactate (Wako Pure Chemical Industries, Ltd., trade name: ethyl lactate)
F-3: Methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 2-butanone)
F-4: N, N-dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd., trade name: N, N-dimethylacetamide)

<Evaluation of resolution>
The photosensitive resin composition was spin-coated on a 6-inch silicon wafer and heated on a hot plate at 120 ° C. for 3 minutes to prepare a coating film having a thickness of 5 μm. The prepared coating film was subjected to reduced projection exposure through a mask with i-line (365 nm) using an i-line stepper (Canon FPA-3000iW). As the mask, a mask having a pattern in which the width of the exposed part and the unexposed part is 1: 1 is from 2 μm: 2 μm to 30 μm: 30 μm in 1 μm increments. The exposure amount is in the range of 100~1100mJ / cm ^2, was subjected to the reduction projection exposure while changing by 100 mJ / cm ^2.

  Next, the exposed coating film was heated at 85 ° C. for 4 minutes (post-exposure baking). A 2.38 mass% tetramethylammonium hydroxide aqueous solution (Tama Chemical Co., Ltd., trade name: TMAH 2.38%) is used as a developer, and a developing machine (Takizawa Sangyo Co., Ltd., trade name: AD-1200) is used. Is sprayed with a developer at 23 ° C. (pump discharge pressure [developer]: 0) on the photosensitive layer (coating film) in a time corresponding to four times the shortest development time (minimum time for removing the unexposed portion). .16 MPa) to remove the unexposed area. Subsequently, 23 ° C. purified water (trade name: purified water, manufactured by Wako Pure Chemical Industries, Ltd.) is sprayed as a rinsing solution for 60 seconds (pump discharge pressure [rinsing solution]: 0.12 to 0.14 MPa), and a developing solution. Washed away. And it was made to dry and the resin pattern was formed. Next, the resin pattern was cured by heat treatment at 180 ° C. for 60 minutes in a solvent drying safety specification thermostat (trade name: HG220, manufactured by Enomoto Kasei Co., Ltd.). The formed resin pattern was observed by enlarging the magnification to 1000 times using a metal microscope. Among the patterns in which the space portion (unexposed portion) was removed cleanly and the line portion (exposed portion) was formed without causing meandering or chipping, the smallest space width value was evaluated as the minimum resolution. The evaluation results are shown in Table 1.

<Evaluation of HAST resistance>
The photosensitive resin composition was spin-coated on a 6-inch silicon wafer and heated on a hot plate at 120 ° C. for 3 minutes to prepare a coating film having a thickness of 5 μm. The prepared coating film was subjected to reduced projection exposure with an i-line stepper (Canon FPA-3000iW) with i-line (365 nm) through a mask and an exposure amount of 1000 mJ / cm ² . As the mask, a comb pattern having a line (exposed portion) / space (unexposed portion) of 100 μm / 10 μm was used.

  Next, the exposed coating film was heated at 85 ° C. for 4 minutes (post-exposure baking). A 2.38 mass% tetramethylammonium hydroxide aqueous solution (Tama Chemical Co., Ltd., trade name: TMAH 2.38%) is used as a developer, and a developing machine (Takizawa Sangyo Co., Ltd., trade name: AD-1200) is used. Is sprayed with a developer at 23 ° C. (pump discharge pressure [developer]: 0) on the photosensitive layer (coating film) in a time corresponding to four times the shortest development time (minimum time for removing the unexposed portion). .16 MPa) to remove the unexposed area. Subsequently, 23 ° C. purified water (trade name: purified water, manufactured by Wako Pure Chemical Industries, Ltd.) is sprayed as a rinsing solution for 60 seconds (pump discharge pressure [rinsing solution]: 0.12 to 0.14 MPa), and a developing solution. Washed away. And it was made to dry and the resin pattern was formed. Next, the resin pattern was cured by heat treatment at 180 ° C. for 60 minutes in a solvent drying safety specification thermostat (trade name: HG220, manufactured by Enomoto Kasei Co., Ltd.).

  Next, a sputtering metal film (seed metal layer) of titanium was formed with a thickness of 0.1 μm on the exposed portion of the obtained silicon wafer and the exposed portion of the resin pattern using a sputtering apparatus. Next, a copper sputtered metal film was formed to a thickness of 0.1 μm. Furthermore, copper sulfate electrolytic plating was performed on the sputtered film. Thereafter, an annealing process was performed at 180 ° C. for 60 minutes to form a conductor layer (titanium layer and copper layer) having a thickness of 10 μm on the exposed portion of the silicon wafer and the exposed portion of the resin pattern. Next, the obtained conductor layer was polished by CMP using a polishing apparatus and an abrasive at a polishing pressure of 13 kPa to expose the resin pattern, thereby forming a conductor pattern embedded in the resin pattern. Next, the exposed portions of the resin pattern and the conductor pattern were covered with a 30 μm thick solder resist to obtain an evaluation substrate.

Using the obtained evaluation substrate, a test was performed for 100 hours under conditions of 130 ° C., 85% RH, and 3.3 V. The resistance value at each time was measured, and when the resistance value was 1 × 10 ⁻⁶ or less, it was determined as a short circuit defect, and the HAST resistance was evaluated according to the following criteria. The evaluation results are shown in Table 1.
“A”: No short circuit occurred for 100 hours.
“B”: A short circuit occurred in less than 100 hours.

  DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Photosensitive layer, 3 ... Circuit groove, 4 ... Resin pattern, 5 ... Seed metal layer, 6 ... Plating layer, 7 ... Conductive layer, 8 ... Conductor pattern.

Claims (4)

(A) component: resin having phenolic hydroxyl group,
(B) component: a compound having a methylol group or an alkoxyalkyl group,
(C) component: an aliphatic compound having two or more functional groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group,
(D) component: Photosensitive acid generator, and
(F) Component: Photosensitive resin composition containing at least one solvent selected from the group consisting of ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, lactic acid ester and γ-butyrolactone.   (E) Component: The photosensitive resin composition of Claim 1 which further contains the compound which has a Si-O bond.   The photosensitive resin composition of Claim 2 whose said (E) component is a silane coupling agent. (A) applying the photosensitive resin composition according to any one of claims 1 to 3 on a substrate, and drying the photosensitive resin composition to form a photosensitive layer;
(B) exposing the photosensitive layer in a predetermined pattern, developing, and further heat-treating to obtain a resin pattern;
(C) forming a conductor layer by plating the exposed portion of the substrate and the exposed portion of the resin pattern;
(D) removing a part of the conductor layer to form a conductor pattern;
A method of manufacturing a circuit board comprising:

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